Skip to main content
Log in

A conductometric study of complexation reaction between dibenzo-24-crown-8 with yttrium cation in some binary mixed non-aqueous solvents

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

The complexation reaction of macrocyclic ligand, dibenzo-24-crown-8 (DB24C8) with Y+3 cation was studied in some binary mixtures of methanol (MeOH), ethanol (EtOH), acetonitrile (AN) and tetrahydrofuran (THF) with dimethylformamide (DMF) at different temperatures using the conductometric method. The conductance data show that in all solvent systems, the stoichiometry of the complex formed between DB24C8 and Y+3 cation is 1:1 (ML). The stability order of (DB24C8.Y)+3 complex in pure non-aqueous solvents was found to be: AN > EtOH > MeOH > DMF. A non-linear behaviour was observed for changes of log Kf of (DB24C8.Y)+3 complex versus the composition of the binary mixed solvents, which was explained in terms of solvent–solvent interactions and also the heteroselective solvation of the species involved in the complexation reaction. The obtained results show that the stability of (DB24C8.Y)+3 complex is sensitive to the mixed solvents composition. The values of thermodynamic parameters (∆H°c and ∆S°c) for formation of (DB24C8.Y)+3 complex were obtained from temperature dependence of the stability constant using the van’t Hoff plots. The results show that in most cases, the (DB24C8.Y)+3 complex is enthalpy destabilized but entropy stabilized and the values and also the sign of thermodynamic parameters are influenced by the nature and composition of the mixed solvents.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Hiraoka, M.: Crown Compounds. Their Characteristics and Applications. Kodansha, Tokyo (1982)

    Google Scholar 

  2. Izatt, R.M., Bradshaw, J.S., Nielsen, S.A., Lamb, J.D., Christensen, J.J.: Thermodynamic and kinetic data for cation-macrocycle interaction. Chem. Rev. 85, 271–339 (1985). doi:10.1021/cr00068a003

    Article  CAS  Google Scholar 

  3. Izatt, R.M., Pawlak, K., Bradshaw, J.S.: Thermodynamic and kinetic data for macrocycle interaction with cations and anions. Chem. Rev. 91, 1721–2085 (1991). doi:10.1021/cr00008a003

    Article  CAS  Google Scholar 

  4. De Boer, J.A.A., Reinhoudt, D.N., Harkema, S., Van Hummel, G.J., De Jong, F.: Thermodynamic constants of complexes of crown ethers and uncharged molecules and X-ray structure of the 18-crown-6(CH3NO2)2 complex. J. Am. Chem. Soc. 104, 4073–4076 (1982). doi:10.1021/ja00379a006

    Google Scholar 

  5. Mosier-Boss, P.A., Popov, A.I.: NMR and infrared studies of the complexation reaction of 18-crown-6 with some organic solvents. J. Am. Chem. Soc. 107, 6168–6174 (1985). doi:10.1021/ja00308a004

    Article  CAS  Google Scholar 

  6. Gholivand, M.B., Shamsipur, M.: Spectroscopic study of the complexation of benzo-15-crown-5 and dibenzo-30-crown-10 with sodium and potassium ions in binary acetonitrile-water mixture. Inorg. Chim. Acta 121, 53–56 (1986). doi:10.1016/S0020-1693(00)87739-7

    Article  CAS  Google Scholar 

  7. Kinisinger, J.B., Tannahill, M.M., Greenberg, M.S., Popov, A.I.: Dimethyl sulfoxide association in dimethyl sulfoxide-pyridine mixtures. Infrared and light scattering spectroscopy. J. Phys. Chem. 77, 2444–2449 (1973). doi:10.1021/j100639a017

    Article  Google Scholar 

  8. Burger, K.: Ionic Solvation and Complex Formation Reactions in Non-Aqueous Solvents. Akademia Kiado, Budapest (1983)

    Google Scholar 

  9. Marcus, Y.: Ionic Solvation. Wiley, Chichester (1985)

    Google Scholar 

  10. Takeda, Y.: A conductance study of alkali metal ion-18-crown-6 complexes in N,N-dimethylformamide. Bull. Chem. Soc. Jpn. 54, 3133–3136 (1981). doi:10.1246/bcsj.54.3133

    Article  CAS  Google Scholar 

  11. D’Aprano, A., Sesta, B.: Complexation of diaza crown compounds with some alkali metal ions in acetonitrile and in methanol at 25 °C. J. Phys. Chem. 99, 2415–2422 (1987). doi:10.1021/j100293a042

    Google Scholar 

  12. Rounaghi, G.H., Chamsaz, M., Nezhadali, A.: Study of complex formation between 18-crown-6 and Pb+2, Tl+2 and Cd+2 cations in binary aqueous/non-aqueous solvents using polarographic techniques (DPP and SWP). J. Incl. Phenom. 38, 153–161 (2000). doi:10.1023/A:1008116218770

    Article  CAS  Google Scholar 

  13. Rounaghi, G.H., Razavipanah, E.: Complexation of 4′-nitrobenzo-15-crown-5 with Li+, Na+, K+, and NH +4 cations in acetonitrile–methanol binary solutions. J. Incl. Phenom. 61, 313–318 (2008). doi:10.1007/s10847-008-9424-6

    Article  CAS  Google Scholar 

  14. Taghdiri, M., Rofouei, M.K., Shamsipur, M.: Conductance study of the thermodynamics of complexation of K+, Rb+, Cs+ and Tl+ ions with dibenzo-24-crown-8 in binary acetonitrile nitromethane mixtures. J. Incl. Phenom. 58, 181–186 (2007). doi:10.1007/s10847-006-9142-x

    Article  CAS  Google Scholar 

  15. Rounaghi, G.H., Sanavi Khoshnood, R., Arbab Zavvar, M.H.: Study of complex formation between N-Phenylaza-15-crown-5 with Mg+2, Ca+2, Ag+ and Cd+2 metal cations in some binary mixed aqueous and non-aqueous solvents using the conductometric method. J. Incl. Phenom. 55, 247–252 (2006). doi:10.1007/s10847-005-9041-6

  16. Khayatian, G., Shamsipur, M., Shariati, S.: Conductance study of the thermodynamics of binding of some macrocyclic polyethers with Tl+ ion in dimethylformamide-acetonitrile mixtures. J. Incl. Phenom. 45, 117–121 (2003). doi:10.1023/A:1023024206317

    Article  CAS  Google Scholar 

  17. Chantooni, M.K., Jr., Kolthoff, M.I.: Relation between stability constants of metal ion cryptates in two solvents and the transfer activity coefficients of the metal ions. J. Solution Chem. 14, 1–12 (1985). doi:10.1007/BF00646725

    Google Scholar 

  18. Rounaghi, G.H., Mofazzeli, F.: Study of complex formation between dicyclohexano-18-Crown-6 (DCH18C6) with Mg2+, Ca2+, Sr2+, and Ba2+ cations in methanol–water binary mixtures using conductometric method. J. Incl. Phenom. 51, 205–210 (2005). doi:10.1007/s10847-004-5691-z

    Article  CAS  Google Scholar 

  19. Cox, B.G., Stroka, J., Schnider, H.: Kinetic studies and thermodynamic results for complex formation and solvation of thallium(I) cryptates in acetonitrile and in acetonitrile-water mixtures. Inorg. Chim. Acta 147, 9–15 (1988). doi:10.1016/S0020-1693(00)80623-4

    Article  CAS  Google Scholar 

  20. Lada, E., Xiubin, L., Kalinowski, M.: Electrochemical study of 18-crown-6-Tl+ complexes in binary solvent mixtures. Monatsh. Chem. 123, 425–433 (1992). doi:10.1007/BF00817598

    Article  CAS  Google Scholar 

  21. Bradshaw, J.S., Maas, G.E., Lamb, J.D., Izatt, R.M., Christensen, J.J.: Cation complexing properties of synthetic macrocyclic polyether-diester ligands containing the pyridine subcyclic unit. J. Am. Chem. Soc. 102, 467–474 (1980). doi:10.1021/ja00522a004

    Article  CAS  Google Scholar 

  22. Benken, R., Bushmann, H.: cis-Benzenetrioxid, 9-crown-3 and 12-crown-4 as ligands for the complexation of cations in different solvents. Inorg. Chim. Acta 134, 49–52 (1987). doi:10.1016/S0020-1693(00)84455-2

    Article  CAS  Google Scholar 

  23. Ansarifard, M., Rounaghi, G.H.: A thermodynamic study between 18-crown-6 with Mg2+, Ca2+, Sr2+ and Ba2+ cations in water–methanol and water–ethanol binary mixtures using the conductometric method. J. Incl. Phenom. 52, 39–44 (2005). doi:10.1007/s10847-004-7162-y

    Article  CAS  Google Scholar 

  24. Rounaghi, G.H., Gerey, N.G., Kazemi, M.S.: A conductometric study of complexation reactions between dibenzo-18-crown-6 (DB18C6) with Cu2+, Zn2+, Tl+ and Cd2+ metal cations in dimethylsulfoxide-ethylacetate binary mixtures. J. Incl. Phenom. 55, 167–172 (2006). doi:10.1007/s10847-005-9033-6

    Article  CAS  Google Scholar 

  25. Rounaghi, G.H., Soleamani, A., Sanavi, K.R.: Conductance studies on complex formation between aza-18-crown-6 with Ag+, Hg+2 and Pb+2 cations in DMSO–H2O binary solutions. J. Incl. Phenom. 58, 43–50 (2007). doi:10.1007/s10847-005-9035-4

    Article  CAS  Google Scholar 

  26. Rounaghi, G.H., Popov, A.I.: 133Cs NMR study of Cs+ ion complexes with dibenzo-21-crown-7 and dibenzo-24-crown-8 in some mixed solvents. Polyhedron 5, 1329–1333 (1986). doi:10.1016/S0277-5387(00)83124-1

    Article  CAS  Google Scholar 

  27. Nakamura, H., Takagi, M., Ueno, K.: Complexation and extraction of alkali metal ions by 4′-picrylaminobenzo-18-crown-6 derivatives. Anal. Chem. 52, 1668–1671 (1980). doi:10.1021/ac50061a030

    Article  CAS  Google Scholar 

  28. Rounaghi, G.H., Sarafraz, A., Monsef, Z.: A polarographic study of Tl+, Pb+2 and Cd+2 complexes with dicyclohexano-18-Crown-6 in some binary mixed solvents. J. Incl. Phenom. 43, 231–237 (2002). doi:10.1023/A:1021283200802

    Article  CAS  Google Scholar 

  29. Monsef, Z., Rounaghi, G.H., Sarafraz, A.: A polarographic study of Tl+, Pb+2 and Cd+2 complexes with aza-18-crown-6 and dibenzopyridino-18-crown-6 in some binary mixed non-aqueous solvents. J. Incl. Phenom. 39, 321–325 (2001). doi:10.1023/A:1011158527265

    Article  CAS  Google Scholar 

  30. Genplot, Computer Graphic Service, USA (1989)

  31. Rounaghi, G.H., Eshaghi, Z., Ghiamati, E.: Thermodynamic study of complex formation between 18-crown-6 and potassium ion in some binary non-aqueous solvents using a conductometric method. Talanta 44, 275–282 (1997). doi:10.1016/S0039-9140(96)02045-0

    Article  CAS  Google Scholar 

  32. Gutmann, V.: The Donor-Acceptor Approach to Molecular Interactions. Plenum press, New York (1978)

    Google Scholar 

  33. Rounaghi, G.H., Popov, A.I.: 133Cs NMR study of the cryptand-222-Cs+ complex in binary solvent mixtures. Polyhedron 5, 1935–1939 (1986). doi:10.1016/S0277-5387(00)87118-1

    Article  CAS  Google Scholar 

  34. Krestov, G.A., Novosyolov, N.P., Perelygin, I.S.: Ionic Solvation. Ellis Horwood, New York (1994)

    Google Scholar 

  35. Rounaghi, G.H., Arbab Zavvar, M.H., Badiee, K., Boosaidi, F., Kazemi, M.S.: A thermodynamic study of complexation of 18-crown-6 with Zn+2, Tl+, Hg+2 and Uo +22 cations in acetonitrile-dimethylformamide binary media and study the effect of anion on the stability constant of (18C6-Na+) complex in methanol solutions. J. Incl. Phenom. 59, 363–369 (2007). doi:10.1007/s10847-007-9338-8

    Article  CAS  Google Scholar 

  36. Rounaghi, G.H., Esmaili Shahri, E., Soleamani, A.: Solvent influence upon complex formation between dibenzo-24-crown-8 and Mg2+, Ca2+, Sr2+ and Ba2+ cations in acetonitrile-dimethylformamide binary mixtures using the conductometric method. J. Chin. Chem. Soc. 51, 923–928 (2004)

    Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge the support of this work by Islamic Azad University, Mashhad Branch, Iran.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Gholam Hossein Rounaghi.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rounaghi, G.H., Tarahomi, S. & Mohajeri, M. A conductometric study of complexation reaction between dibenzo-24-crown-8 with yttrium cation in some binary mixed non-aqueous solvents. J Incl Phenom Macrocycl Chem 63, 319–325 (2009). https://doi.org/10.1007/s10847-008-9525-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-008-9525-2

Keywords

Navigation